US20210230368A1 - Polyimide-based polymer film, substrate for display device, and optical device using the same - Google Patents
Polyimide-based polymer film, substrate for display device, and optical device using the same Download PDFInfo
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- US20210230368A1 US20210230368A1 US15/733,816 US202015733816A US2021230368A1 US 20210230368 A1 US20210230368 A1 US 20210230368A1 US 202015733816 A US202015733816 A US 202015733816A US 2021230368 A1 US2021230368 A1 US 2021230368A1
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- United States
- Prior art keywords
- polyimide
- based resin
- group
- resin film
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 182
- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 230000003287 optical effect Effects 0.000 title claims abstract description 34
- 239000004642 Polyimide Substances 0.000 claims abstract description 150
- 239000011347 resin Substances 0.000 claims abstract description 108
- 229920005989 resin Polymers 0.000 claims abstract description 108
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- -1 acid anhydride compound Chemical class 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims description 78
- 125000000524 functional group Chemical group 0.000 claims description 76
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 25
- 230000008859 change Effects 0.000 claims description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000005567 fluorenylene group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- MHAUGLFOVCQYNR-UHFFFAOYSA-N pentaphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 MHAUGLFOVCQYNR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 77
- 238000001723 curing Methods 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 0 *CN1C(=O)C2(C(=O)N(*)C2=O)C1=O Chemical compound *CN1C(=O)C2(C(=O)N(*)C2=O)C1=O 0.000 description 11
- 229920005575 poly(amic acid) Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
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- 239000009719 polyimide resin Substances 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000004429 atom Chemical group 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
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- 125000005462 imide group Chemical group 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
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- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FMACFWAQBPYRFO-UHFFFAOYSA-N 5-[9-(1,3-dioxo-2-benzofuran-5-yl)fluoren-9-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 FMACFWAQBPYRFO-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- GMLIPSXOERVACV-UHFFFAOYSA-N C.C.C.C.C1=CC=C([Ar]C2=CC=CC=C2)C=C1 Chemical compound C.C.C.C.C1=CC=C([Ar]C2=CC=CC=C2)C=C1 GMLIPSXOERVACV-UHFFFAOYSA-N 0.000 description 2
- ACZOIRSHLMURLN-UHFFFAOYSA-N C.C.C1=CC=C(C2=CC=C(C3=CC=CC=C3)C=C2)C=C1.CC.CC.CC Chemical compound C.C.C1=CC=C(C2=CC=C(C3=CC=CC=C3)C=C2)C=C1.CC.CC.CC ACZOIRSHLMURLN-UHFFFAOYSA-N 0.000 description 2
- LGDRGJPCCOBVLS-UHFFFAOYSA-N C1=CC=C(CC2=CC=CC=C2)C=C1.CC(=O)OC(C)=O.CC(=O)OC(C)=O Chemical compound C1=CC=C(CC2=CC=CC=C2)C=C1.CC(=O)OC(C)=O.CC(=O)OC(C)=O LGDRGJPCCOBVLS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AESLWNQXGHIIQV-UHFFFAOYSA-N FC(F)(F)C1=C(C2=CC=C(C3=C(C(F)(F)F)C=CC=C3)C=C2)C=CC=C1 Chemical compound FC(F)(F)C1=C(C2=CC=C(C3=C(C(F)(F)F)C=CC=C3)C=C2)C=CC=C1 AESLWNQXGHIIQV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
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- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/02—Alignment layer characterised by chemical composition
- C09K2323/027—Polyimide
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
Definitions
- each heat treatment step is performed at a temperature of 400° C. to 450° C., and the total time of each heat treatment step satisfies 130 minutes to 200 minutes.
- a trifluoromethyl group capable of imparting an electron withdrawing effect is introduced as a substituent into a diamine monomer compound used for the synthesis of a polyimide resin, to thereby suppress the formation of charge transfer complex (CTC) of Pi-electrons existing in the imide chain, through which it is possible to secure transparency and realize excellent optical properties.
- CTC charge transfer complex
- a polyimide film was prepared in the same manner as in Example 1, except that pyromellitic dianhydride (PMDA) was used as acid dianhydride instead of Biphenyltetracarboxylic dianhydride (BPDA).
- PMDA pyromellitic dianhydride
- BPDA Biphenyltetracarboxylic dianhydride
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
- This application is a 35 U.S.C. 371 National Phase Entry Application from PCT/KR2020/001263, filed on Jan. 28, 2020, designating the United States, which claims the benefit of priority from Korean Patent Application No. 10-2019-0013486 filed on Feb. 1, 2019; Korean Patent Application No. 10-2019-0121176 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0121177 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0121178 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0161494 filed on Dec. 6, 2019; and Korean Patent Application No. 10-2019-0161495 filed on Dec. 6, 2019 in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.
- The present disclosure relates to a polyimide-based resin film capable of ensuring excellent optical properties even under high temperature heat treatment conditions, and stably maintaining optical properties even during further heat treatment, a substrate for display device and an optical device using the same.
- The display device market is rapidly changing based on flat panel displays (FPDs) that are easy to fabricate over a large area and can be reduced in thickness and weight. Such flat panel displays include liquid crystal displays (LCDs), organic light emitting displays (OLEDs), or electrophoretic devices.
- In line with recent efforts to further extend the application and use of flat panel displays, particular attention has focused on so-called flexible display devices in which flexible substrates are applied to flat panel displays. The application of such flexible display devices is particularly reviewed based on mobile devices such as smart phones and the application fields thereof are gradually extended.
- In general, in manufacturing a flexible display device and an illumination device, a TFT device is manufactured by forming a multilayer inorganic film such as a buffer layer, an active layer, and a gate insulator on the cured polyimide.
- However, when light is emitted to the polyimide layer (substrate layer), the emission efficiency may be reduced due to the difference between the refractive index of the multilayer upper layer made of the inorganic film and the refractive index of the polyimide layer.
- In addition, when the polyimide material included in the polyimide layer (substrate layer) is cured at a high temperature of 400° C. or more, optical properties may decrease due to deterioration of the polyimide.
- Accordingly, there is a demand for developing a new polyimide that can satisfy high heat resistance and excellent optical properties.
- The present disclosure provides a polyimide-based resin film capable of ensuring excellent optical properties even under high temperature heat treatment conditions, and stably maintaining optical properties even during further heat treatment.
- The present disclosure also provides a substrate for display device and an optical device using the same.
- In order to achieve the above objects, one aspect of the present disclosure provides a polyimide-based resin film comprising a polyimide-based resin containing a polyimide repeating unit represented by the following Chemical Formula 1, wherein an absolute value of a change in yellow index (ΔYI) obtained by the following Equation 1 is 4 or less.
- in Chemical Formula 1, X1 is a tetravalent functional group represented by the following Chemical Formula 2, Y1 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,
- in Chemical Formula 2, Ar is a polycyclic aromatic divalent functional group,
-
Change in Yellow Index (ΔYI)=YI f −YI 0 [Equation 1] - in Equation 1, YIf is the final yellow index of the film obtained after heat-treating the polyimide-based resin film at a temperature of 400° C. to 450° C. 130 minutes to 200 minutes, and YI0 is a yellow index of the polyimide-based resin film before the heat treatment.
- Another aspect of the present disclosure provides a substrate for display device comprising the polyimide-based resin film.
- A further aspect of the present disclosure provides an optical device comprising the polyimide-based resin film.
- Hereinafter, a polyimide-based resin film according to specific embodiments of the present disclosure, a substrate for a display device and an optical device using the same will be described in more detail.
- Unless otherwise specified throughout this specification, the technical terms used herein are only for reference to specific embodiments and is not intended to limit the present disclosure.
- The singular forms “a”, “an”, and “the” used herein include plural references unless the context clearly dictates otherwise.
- The term “including” or “comprising” used herein specifies a specific feature, region, integer, step, action, element and/or component, but does not exclude the presence or addition of a different specific feature, region, integer, step, action, element, component and/or group.
- The terms including ordinal numbers such as “a first”, “a second”, etc. are used only for the purpose of distinguishing one component from another component, and are not limited by the ordinal numbers. For instance, a first component may be referred to as a second component, or similarly, the second component may be referred to as the first component, without departing from the scope of the present invention.
- In the present specification, the (co)polymer means including both a polymer and a copolymer, the polymer means a homopolymer consisting of a single repeating unit, and the copolymer means a composite polymer containing two or more repeating units.
- In the present specification, examples of the substituents are described below, but are not limited thereto.
- In the present specification, the term “substituted” means that other functional groups instead of a hydrogen atom in the compound are bonded, and a position to be substituted is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same as or different from each other.
- In the present specification, the term “substituted or unsubstituted.” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxy group: a sulfonic acid group: a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkyithioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or being unsubstituted or substituted with a substituent to which two or more substituents are linked among the substituents exemplified above. For example, “the substituent to which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may also be an aryl group, and may be interpreted as a substituent to which two phenyl groups are linked.
- In the present specification, the notation
- In the present specification, aromatic is a property that satisfies Huckle's Rule, and a compound can be defined as aromatic if all of the following three conditions are satisfied according to Huckle's Rule.
- 1) There must be 4n+2 electrons that are completely conjugated by empty p-orbitals, unsaturated bonds, lone electron pairs, etc.
- 2) 4n+2 electrons have to form planar isomers and form a ring structure.
- 3) All atoms of the ring have to be able to participate in conjugation.
- In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be a straight-chain or a branched-chain. The number of carbon atoms of the straight chain alkyl group is not particularly limited, but is preferably 1 to 20. Also, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are the same as described above.
- In the present specification, the haloalkyl group means a functional group in which the above-described alkyl group is substituted by a halogen group, and examples of halogen group are fluorine, chlorine, bromine or iodine. The haloalkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are the same as described above.
- In the present specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound are removed, and for example, it may be a divalent functional group, a trivalent functional group, and a tetravalent functional group. As an example, a tetravalent functional group derived from a cyclobutane means a residue in which any four hydrogen atoms bonded to the cyclobutane are removed.
- In the present specification, the electron-withdrawing group may include one or more selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group, and a sulfonyl group, and preferably, it may be a haloalkyl group such as trifluoromethyl group (—CF3).
- In the present specification, a direct bond or a single bond means being connected to a bond line in which no atoms or atomic groups exist at the corresponding position.
- Specifically, it means the case where no other atoms exist in the parts represented as L1, or L2 in Chemical Formula.
- In the present specification, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC method. In the process of determining the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzing device, a detector such as a refractive index detector, and an analytical column can be used. Commonly applied conditions for temperature, solvent, and flow rate can be used. Specific examples of the measurement condition are as follows: Waters PL-GPC220 instrument with Polymer Laboratories PLgel M-B, 300 mm column was used, the evaluation temperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent, the flow rate is 1 mL/min, samples were prepared at a concentration of 10 mg/10 mL and then fed in an amount of 200 μL, and the values of Mw could be determined using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standards used herein was 9 types of 2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000.
- Hereinafter, the present disclosure will be described in more detail.
- 1. Polyimide Film
- According to one embodiment of the present disclosure, there can be provided a polyimide-based resin film comprising a polyimide-based resin containing a polyimide repeating unit represented by Chemical Formula 1, wherein an absolute value of a change in yellow index (ΔYI) obtained by Equation 1 is 4 or less.
- The present inventors have found through experiments that as in the polyimide-based resin film of the one embodiment, a tetravalent functional group derived from tetracarboxylic dianhydride and an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, having a specific structure as shown in Chemical Formula 2, is contained within the polyimide-based repeating unit structure, and thereby, the polyimide resin film subjected to curing at a high temperature of 400° C. or more has excellent optical properties, thereby completing the present disclosure. In particular, since the polyimide-based resin includes a reaction product obtained through imidization reaction of a tetracarboxylic dianhydride containing a structure represented by Chemical Formula 2 and an aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, it is considered that high heat resistance is secured by the physical and chemical action according to the novel structure of the acid anhydride monomer and the aromatic diamine monomer, so that excellent optical properties are achieved not only in the cured film through heat treatment at a high temperature of 400° C. or more but also during additional heat treatment for the cured film at an elevated temperature of 400° C. or more.
- Specifically, trifluoromethyl group (—CF3) capable of imparting an electron withdrawing effect is introduced as a substituent into a diamine monomer compound used for the synthesis of a polyimide resin, to thereby suppress the formation of charge transfer complex (CTC) of Pi-electrons existing in the imide chain, through which it is possible to secure transparency and realize excellent optical properties.
- Moreover, a polyimide-based resin synthesized from an aromatic diamine monomer having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted improves the ordering and orientation properties between molecules and ensure sufficient heat resistance even in the polyimide film obtained by high temperature curing, and when this is used as a plastic substrate, it can prevent the plastic substrate from being damaged by heat when heat treating the metal layer formed on the plastic substrate, and also realize excellent optical properties even during additional heat treatment at a high temperature of 400° C. or more.
- Specifically, the polyimide film according to the present disclosure can increase the refractive index, can be used as a substrate layer in the flexible display device, and can reduce the difference in refractive index with each layer constituting the device, from which the amount of light internally dissipated is reduced and the efficiency of bottom emission can be effectively increased.
- The polyimide-based resin is meant to include both a polyimide, and a precursor polymer thereof such as polyamic acid or polyamic acid ester. That is, the polyimide-based polymer may include one or more selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. That is, the polyimide-based polymer may include one type of polyamic acid repeating unit, one type of polyamic acid ester repeating unit, one type of polyimide repeating unit, or a copolymer in which these two or more types of repeating units are mixed.
- The one or more repeating units selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit may form a main chain of the polyimide-based polymer.
- In particular, the polyimide-based resin may include a polyimide repeating unit represented by Chemical Formula 1.
- In Chemical Formula 1, X1 is a tetravalent functional group represented by Chemical Formula 2, the X1 is a functional group derived from a tetracarboxylic dianhydride compound used in the synthesis of a polyimide-based resin.
- In Chemical Formula 2, Ar is a polycyclic aromatic divalent functional group. The polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound or a derivative compound thereof, and may include a fluorenylene group. The derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.
- More specifically, in Ar of Chemical Formula 2, the polycyclic aromatic divalent functional group may include a fused cyclic divalent functional group containing at least two or more aromatic cyclic compounds. That is, the polycyclic aromatic divalent functional group may contain at least two or more aromatic ring compounds in the functional group structure, and also the functional group may have a fused ring structure.
- The aromatic cyclic compound may include an arene compound containing one or more benzene rings, or a hetero arene compound in which carbon atoms in the arene compound are replaced with heteroatoms.
- The aromatic cyclic compound may contain at least two or more in the polycyclic aromatic divalent functional group, and each of the two or more aromatic cyclic compounds may directly form a fused ring, or may form a fused ring via another ring structure. As an example, when two benzene rings are each fused to a cycloalkyl ring structure, it may be defined that two benzene rings form a fused ring via each cycloalkyl ring.
- The fused cyclic divalent functional group containing at least two or more aromatic cyclic compounds is a divalent functional group derived from a fused cyclic compound or a derivative compound thereof containing at least two or more aromatic cyclic compounds, and the derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.
- Examples of the polycyclic aromatic divalent functional group are not particularly limited, but as an example, a fluorenylene group can be mentioned.
- Examples of the tetravalent functional group represented by Chemical Formula 2 includes a functional group represented by the following Chemical Formula 2-1.
- In Chemical Formula 1, Y1 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, the Y1 may be a functional group derived from a diamine compound used in the synthesis of polyamic acid, polyamic acid ester, or polyimide.
- In the Y1, the aromatic divalent functional group having 15 or more carbon atoms may include three or more aromatic cyclic compounds. As three or more aromatic cyclic compounds are contained in this way, the polyimide-based resin has improved ordering and orientation properties between molecules, and thus, it can ensure sufficient heat resistance even in a polyimide film obtained by high-temperature curing.
- The aromatic divalent functional group having 15 or more carbon atoms may include one or more selected from the group consisting of a triphenylene group, a quarterphenylene group, and a pentaphenylene group.
- The electron-withdrawing group may include one or more selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group, and a sulfonyl group.
- As an electron-withdrawing substituent such as trifluoromethyl group (—CF3) having high electronegativity are substituted, the effect of suppressing the formation of CTC (charge transfer complex) of Pi-electrons existing in the polyimide resin chain is increased, thereby ensuring improved transparency. That is, the packing in the polyimide structure or between the chains can be reduced, and due to steric hindrance and electrical effects, it is possible to weaken the electrical interaction between the chromophores and show high transparency in the visible region.
- More specifically, the aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing functional group of the Y1 is substituted may include a functional group represented by the following Chemical Formula 3.
- in Chemical Formula 3, T1 to T3 are the same as or different from each other, and each independently, an electron-withdrawing group, m1 to m3 are the same as or different from each other, at least one of m1 to m3 is an integer of 1 to 4, the rest are an integer of 0 to 4, and n is an integer of 1 to 10.
- The aromatic divalent functional group having 15 or more carbon atoms in which at least one electron withdrawing group of the Y1 is substituted may include a functional group represented by the following Chemical Formula 3-1.
- The polyimide-based resin may include a combination of a tetracarboxylic dianhydride represented by the following Chemical Formula 4 and an aromatic diamine having 15 or more carbon atoms in which at least one electron withdrawing group is substituted.
- in Chemical Formula 4, Ar′ is a polycyclic aromatic divalent functional group. The polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound, and may include a divalent functional group derived from a fluorenylene group or derivative compound thereof, fluorenylene group. The derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.
- Specific examples of the tetracarboxylic dianhydride represented by Chemical Formula 4 include 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
- The aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted is a compound in which an amino group (—NH2) is bonded to both terminals of the aromatic divalent functional group having 15 or more carbon atoms in which at least one of the above-mentioned electron-withdrawing groups is substituted. The details of the aromatic divalent functional group having 15 or more carbon atoms in which at least one of the above-mentioned electron-withdrawing groups is substituted are the same as described above.
- Specific examples of the aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted may include a diamine represented by the following Chemical Formula a.
- More specifically, in the polyimide-based resin, a bond between the nitrogen atom of the amino group and the carbon atom of the anhydride group may be formed by a reaction between a terminal anhydride group (—OC—O—CO—) of the tetracarboxylic dianhydride represented by Chemical Formula 4, and a terminal amino group (—NH2) of the aromatic diamine having 15 or more carbon atoms in which at least one of the electron withdrawing group is substituted.
- The polyimide-based resin may further include a polyimide repeating unit represented by the following Chemical Formula 5.
- in Chemical Formula 5, X2 is one of the tetravalent functional groups represented by the following Chemical Formula 6, and Y2 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,
- in Chemical Formula 6, R1 to R6 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, L is any one selected from the group consisting of a single bond, —O—, —CO—, —COO—, —S—, —SO—, —SO2—, —CR7R8—, —(CH2)t—, —O(CH2)tO—, —COO(CH2)tOCO—, —CONH—, phenylene or a combination thereof, where R7 and R8 are each independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, and t is an integer of 1 to 10.
- Specific examples of the functional group represented by Chemical Formula 6 include a functional group represented by the following Chemical Formula 6-1, a functional group represented by the following Chemical Formula 6-2, or a functional group represented by the following Chemical Formula 6-3.
- That is, the polyimide-based polymer may include a first repeating unit containing a repeating unit represented by Chemical Formula 1 wherein the repeating unit derived from tetracarboxylic dianhydride is a functional group represented by Chemical Formula 2; and a second repeating unit containing a repeating unit represented by Chemical Formula 5 wherein the repeating unit derived from tetracarboxylic dianhydride is a functional group represented by Chemical Formula 6. The first repeating unit and the second repeating unit can be randomly arranged in the polyimide-based polymer to form a random copolymer, or form a block copolymer by forming a block of the first repeating unit and a block of the second repeating unit.
- The polyimide-based polymer including the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 5 can be prepared by reacting two or more different tetracarboxylic dianhydride compounds with a diamine compound, and the two types of tetracarboxylic dianhydrides can be added simultaneously to synthesize a random copolymer, or can be added sequentially to synthesize a block copolymer.
- The polyimide repeating unit represented by Chemical Formula 5 may be contained in an amount of 1 mol % or more and 99 mol % or less with respect to the total repeating units contained in the polyimide-based resin.
- The polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5 may be contained in an amount of 70 mol % or more, or 80 mol % or more, or 90 mol % or more, or 70 mol % or more and 100 mol % or less, 80 mol % or more and 100 mol % or less, 70 mol % or more and 90 mol % or less, 70 mol % or more and 99 mol % or less, 80 mol % or more and 99 mol % or less, 90 mol % or more and 99 mol % or less with respect to the total repeating units contained in the polyimide-based resin.
- That is, the polyimide-based resin is composed of only the polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5, or most thereof can be composed of the polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5.
- More specifically, the polyimide-based resin may not be mixed with other diamines in addition to diamines capable of inducing aromatic divalent functional groups having 15 or more carbon atoms in which at least one of the electron-withdrawing group is substituted, or may be mixed in an extremely small amount of less than 1 mol %.
- More specifically, the polyimide repeating unit represented by Chemical Formula 5 may include one or more repeating units selected from the group consisting of a polyimide repeating unit represented by the following Chemical Formula 5-1, a polyimide repeating unit represented by the following Chemical Formula 5-2, and a polyimide repeating unit represented by the following Chemical Formula 5-3.
- in Chemical Formula 5-1, X3 is a tetravalent functional group represented by Chemical Formula 6-1, and Y3 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,
- in Chemical Formula 5-2, X4 is a tetravalent functional group represented by Chemical Formula 6-2, and Y4 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,
- in Chemical Formula 5-3, X5 is a tetravalent functional group represented by Chemical Formula 6-3, and Y3 is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted.
- The weight average molecular weight (measured by GPC) of the polyimide-based resin is not particularly limited, but may be, for example, 1000 g/mol or more and 200000 g/mol or less, or 10000 g/mol or more and 200000 g/mol or less.
- Because the polyimide-based resin according to the present disclosure can exhibit excellent colorless and transparent properties while maintaining properties such as heat resistance and mechanical strength as they are due to a rigid structure, it can be used in a diverse range of fields such as device substrate, display cover substrate, optical film, integrated circuit (IC) package, adhesive film, multilayer FRC (flexible printed circuit), tape, touch panel, protective polymer film for optical disc, etc. In particular, it can be suitable for display cover substrate.
- Meanwhile, the polyimide-based resin film of the one embodiment may include a cured product in which the polyimide-based resin is cured at a temperature of 400° C. or more. The cured product means a material obtained through a curing step of the resin composition containing the polyimide-based resin, and the curing process may be performed at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less for 50 minutes or more and 100 minutes or less.
- More specifically, examples of the method of synthesizing the polyimide-based resin film are not particularly limited, and, for example, a method of manufacturing a film including a step of coating a resin composition containing the polyimide-based resin onto a substrate to form a coating film (step 1); a step of drying the coating film (step 2); and a step of heat-treating and curing the dried coating film (step 3) can be used.
- Step 1 is a step of coating the resin composition containing the above-mentioned polyimide-based resin onto a substrate to form a coating film. The method of coating the resin composition containing the polyimide-based resin onto a substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexographic printing, inkjet, and the like can be used.
- Further, the resin composition containing the polyimide-based resin may be in the form dissolved or dispersed in an organic solvent. In the case of having such form, for example, when the polyimide-based resin is synthesized in the organic solvent, the solution may be the reaction solution thus obtained itself or a solution obtained by diluting the reaction solution with another solvent. Further, when the polyimide-based resin is obtained as powder, the solution may be a solution obtained by dissolving the powder in an organic solvent.
- Specific examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and the like. They can be used alone or in combination of two or more.
- The resin composition containing the polyimide-based resin may include the solid in such an amount that the solution has an appropriate viscosity in consideration of processability such as a coating property during the film forming process. For example, the content of the composition may be adjusted so that the total content of the resin is 5% by weight or more and 25% by weight or less, or may be adjusted to 5% by weight or more and 20% by weight or less, or 5% by weight or more and 15% by weight or less.
- In addition, the resin composition containing the polyimide-based resin may further include other components in addition to the organic solvent. In a non-limiting example, when the resin composition containing the polyimide-based resin is coated, additives capable of improving the uniformity of the film thickness and the surface smoothness, or improving the adhesion with a substrate, or changing the dielectric constant and conductivity, or increasing the denseness, may be further included. Examples of these additives include surfactants, silane-based compounds, dielectrics or crosslinking compounds, etc.
- Step 2 is a step of drying the coating film formed by coating a resin composition containing the polyimide-based resin onto a substrate.
- The step of drying the coating film may be performed by a heating means such as a hot plate, a hot-air circulation furnace, an infrared furnace and the like, and the drying may be performed at a temperature of 50° C. or more and 150° C. or less, or 50° C. or more and 100° C. or less.
- Step 3 is a step of heat-treating and curing the dried coating film. In this case, the heat treatment may be performed by a heating means such as a hot plate, a hot-air circulation furnace, an infrared furnace and the like, and the heat treatment can be performed at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less.
- The thickness of the polyimide-based resin film is not particularly limited, but for example, it cart be freely adjusted within the range of 0.01 μm or more and 1000 μm or less. If the thickness of the polyimide-based resin film increases or decreases by a specific value, the physical properties measured in the polyimide-based resin film may also change by a certain value.
- Meanwhile, the polyimide-based resin film may have an absolute value of a change in yellow index (ΔYI) obtained by the following Equation 1 of 4 or less, or 3.5 or less, or 0.01 or more and 4 or less, or 0.01 or more and 3.5 or less, or 0.05 or more and 4 or less, or 0.05 or more and 3.5 or less, or 0.1 or more and 4 or less, or 0.1 or more and 3.5 or less.
-
Change in Yellow Index (ΔYI)=YI f −YI 0 [Equation 1] - in Equation 1, YIf is a final yellow index of the film obtained after heat-treating the polyimide-based resin film at a temperature of 400° C. to 450° C. 130 minutes to 200 minutes, and YI0 is a yellow index of the polyimide-based resin film before the heat treatment.
- Since the value of a change in yellow index (ΔYI) obtained by Equation 1 can have a negative or positive value, the change in the substantial yellow index due to the additional heat treatment can be compared through the absolute value of the change in yellow index obtained in Equation 1. When the value of a change in yellow index obtained in Equation 1 is a negative value (e.g., −1), the absolute value of a change in yellow index obtained in Equation 1 may be a value from which a negative sign has been removed (e.g., 1). When the value of a change in yellow index obtained in Equation 1 is a positive value (e.g., 1), the absolute value of a change in yellow index obtained in Equation 1 is the same as the value of a change in yellow index obtained in Equation 1 (e.g., 1),
- In the YIf of Equation 1, examples of a method of heat treating the polyimide-based resin film at 400° C. to 450° C. for 130 minutes to 200 minutes are not particularly limited. The heat treatment can be performed in a single stage or can be performed in a multi-stage. In the case of the multi-stage, it cart pass through additional heat treatment in the second to tenth stage, and in this case, each step can be performed continuously or discontinuously.
- However, if the heat treatment is performed sequentially, each heat treatment step is performed at a temperature of 400° C. to 450° C., and the total time of each heat treatment step satisfies 130 minutes to 200 minutes.
- That is, despite the addition of the heat treatment conditions at a high temperature of 400° C. or more for the polyimide-based resin film of the one embodiment, the absolute value of a change in yellow index which is the optical property of the film is 4 or less which is very low, and thus, the polyimide-based resin film of the above one embodiment may realize high heat resistance.
- When the polyimide-based resin film sample used for the measurement of the yellow index is composed of only a pure polyimide-based resin film, the yellow index can be automatically measured through the result of analyzing a polyimide-based resin film sample by a color meter (Color-Eye 7000A, GRETAGMACBETH). For example, a pure polyimide-based resin film can be ensured through the process of peeling a substrate film from a laminate including the substrate film and the polyimide-based resin film coated on the substrate film.
- The yellow index may be that which is measured for the polyimide-based resin film sample of the above-mentioned one embodiment having a thickness of 5 μm or more and 30 μm or less, or 5 μm or more and 15 μm or less, or 8 μm or more and 12 μm or less.
- In Equation 1, the yellow index of the polyimide-based resin film before heat treatment may be 15 or less, or 14.5 or less, or 1 or more and 15 or less, or 1 or more and 14.5 or less, or 5 or more and 15 or less, or 5 or more and 14.5 or less, or 8.8 or more and 14.1 or less. The polyimide-based resin film which is a measurement object of the yellow index of the polyimide-based resin film before heat treatment means a material obtained through the curing process of the resin composition containing the polyimide resin as described above, For example, the curing process may be performed at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less for 50 minutes or more and 100 minutes or less.
- In addition, in Equation 1, the final yellow index of the polyimide-based resin film may be 20 or less, or 18 or less, or 5 or more and 20 or less, or 5 or more and 18 or less, or 8 or more and 20 or less, or 8 or more and 18 or less, or 8.7 or more and 17.6 or less. The polyimide-based resin film which is a measurement object of the final yellow index means a film obtained after further heat-treating the polyimide-based resin film at a temperature of 400° C. to 450° C. e for 130 minutes to 200 minutes as described above, and details of the heat treatment are the same as described above in Equation 1.
- As described above, a trifluoromethyl group (—CF3) capable of imparting an electron withdrawing effect is introduced as a substituent into a diamine monomer compound used for the synthesis of a polyimide resin, to thereby suppress the formation of charge transfer complex (CTC) of Pi-electrons existing in the imide chain, through which it is possible to secure transparency and realize excellent optical properties.
- 2. Substrate for Display Device
- Meanwhile, according to another embodiment of the present disclosure, there can be provided a substrate for display device including the polyimide-based resin film of another embodiment. Details of the polyimide-based resin film may include all of the contents described above in the one embodiment.
- The display device including the substrate may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display), a rollable display or foldable display, or the like.
- The display device may have various structures according to an application field and a specific shape, and may include, for example, a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), a transparent substrate, or the like.
- The polyimide-based resin film of another embodiment described above may be used in various applications such as a substrate, an outer protective film or a cover window in such various display devices, and more specifically, may be applied to a substrate.
- For example, the display device substrate may have a structure in which a device protective layer, a transparent electrode layer, a silicon oxide layer, a polyimide-based resin film, a silicon oxide layer, and a hard coating layer are sequentially stacked.
- The transparent polyimide substrate may further include a silicon oxide layer formed between the transparent polyimide-based resin film and the cured layer in order to further improve the solvent resistance, water permeability and optical properties thereof, and the silicon oxide layer may be produced by curing polysilazane.
- Specifically, the silicon oxide layer may, before forming a coating layer on at least one surface of the transparent polyimide-based resin film, be formed by curing the coated polysilazane after coating and drying a solution containing polysilazane
- The substrate for a display device according to the present disclosure can provide a transparent polyimide cover substrate having solvent resistance, optical properties, water permeability and scratch resistance while having excellent warpage properties and impact resistance by including the above-described device protective layer.
- 3. Optical Device
- Meanwhile, according to another embodiment of the present disclosure, there can be provided an optical device including the polyimide-based resin film of the other embodiment. The details of the polyimide-based resin film may include all of those described above in the one embodiment.
- The optical device may include all kinds of devices using properties realized by light, and may be, for example, a display device. Specific examples of the display device include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, a rollable display or foldable display device, or the like, but is not limited thereto.
- The optical device may have various structures according to the application field and the specific shape, and for example, it may have a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), a transparent substrate, or the like.
- The polyimide-based resin film of another embodiment described above may be used in various applications such as a substrate, an outer protective film or a cover window in various optical devices, and more specifically, may be applied to a substrate.
- According to the present disclosure, a polyimide-based resin film capable of ensuring excellent optical properties even under high temperature heat treatment conditions, and stably maintaining excellent optical properties even during further heat treatment, a substrate for display device, and an optical device using the same can be provided.
- Hereinafter, embodiments of the present disclosure will be described in more detail by way of examples. However, these examples are provided for illustrative purposes only, and are not intended to limit the scope of the present disclosure.
- (1) Preparation of Polyimide Precursor Composition
- The organic solvent DEAc was filled in a reactor under a stream of nitrogen, and then 0.735 mol of a diamine represented by the following Chemical Formula a was added and dissolved at the same temperature while maintaining the temperature of the reactor to 25° C. To the solution to which the diamine represented by the following Chemical Formula a was added, 0.3675 mol of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) represented by Chemical Formula b and 0.3675 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) were added as an acid dianhydride at the same temperature, and stirred for 24 hours to give a polyimide precursor composition.
- (2) Preparation of Polyimide Film
- The polyimide precursor composition was spin coated on a glass substrate. The polyimide precursor composition-coated glass substrate was put in an oven and heated at a rate of 5° C./min, and a curing process was performed by maintaining at 80° C. for 20 minutes and at 450° C. for 70 minutes, thereby preparing a polyimide film (thickness: 10 μm).
- A polyimide film was prepared in the same manner as in Example 1, except that 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) was used as acid dianhydride instead of 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA).
- A polyimide film was prepared in the same manner as in Example 1, except that pyromellitic dianhydride (PMDA) was used as acid dianhydride instead of Biphenyltetracarboxylic dianhydride (BPDA).
- (1) Preparation of Polyimide Precursor Composition
- The organic solvent DEAN was filled in a reactor under a stream of nitrogen, and then 0.735 mol of 2,2′-bis(trifluoromethyl)benzidine (TFMB) was added and dissolved at the same temperature while maintaining the temperature of the reactor to 25° C. To the solution to which 2,2′-bis(trifluoromethyl)benzidine (TFMB) was added, 0.735 mol of 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA) was added as an acid dianhydride at the same temperature, and stirred for 24 hours to give a polyimide precursor composition.
- (2) Preparation of Polyimide Film
- The polyimide precursor composition was spin coated on a glass substrate. The polyimide precursor composition-coated glass substrate was put in an oven and heated at a rate of 5° C./min, and a curing process was performed by maintaining at 80° C. for 20 minutes and at 450° C. for 70 minutes, thereby preparing a polyimide film (thickness: 10 μm).
- A polyimide film was prepared in the same manner as in Comparative Example 1, except that 0.3675 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 0.3675 mol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) were added as an acid dianhydride.
- A polyimide film was prepared in the same manner as in Comparative Example 1, except that 0.3675 mol of pyromellitic dianhydride (PMDA) and 0.3675 mol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) were added as an acid dianhydride.
- The physical properties of the polyimide films obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.
- 1. Yellow Index (YI0) (450° C./70 Min Curing)
- The polyimide film having a thickness of 10 μm obtained in each of Examples and Comparative Examples was peeled from a glass substrate to prepare a sample having a size of width 2 cm×length 10 cm. Then, the yellow index (YI0) was determined for the sample using a color meter (Color-Eye 7000A manufactured by GRETAGMACBETH), and described in Table 1 below.
- 2, Heat Resistant Yellow Index (ΔYI)
- (1) Additional Condition for One High-Temperature Heat Curing (450° C./70 Min→410° C./60 Min Curing)
- The polyimide film having a thickness of 10 μm obtained in each of Examples and Comparative Examples was further cured at 410° C. for 60 minutes, and then was peeled from a glass substrate to prepare a sample having a size of width 2 cm×length 10 cm. Then, the final yellow index (HO was determined for the sample using a color meter (Color-Eye, 7000A, GRETAGMACBETH), and a change in yellow index (ΔYI) was calculated according to the following Equation (1) to obtain a heat-resistant yellow index, and the results are shown in Table 1 below.
- (2) Additional Conditions for Two High Temperature Heat Curing (450° C./70 Min→410° C./60 Min→445° C./60 Min Curing)
- The polyimide film having a thickness of 10 μm obtained in each of Examples and Comparative Examples was further cured at 410° C. for 60 minutes, and then further cured at 445° C. for 60 minutes. The resulting film was peeled from a glass substrate to prepare a sample having a size of width 2 cm×length 10 cm. Then, the final yellow index (YIf) was determined for the sample using a color meter (Color-Eye 7000A, GRETAGMACBETH), and a change in yellow index (ΔYI) was calculated according to the following Equation (1) to obtain a heat-resistant yellow index, and the results are shown in Table 1 below.
- (3) Additional Conditions for Two High Temperature Heat Curing (450° C./70 Min→445° C./30 Min→445° C./30 Min Curing)
- The polyimide film having a thickness of 10 μm obtained in each of Examples and Comparative Examples was further cured at 445° C. for 30 minutes, and then further cured at 445° C. for 30 minutes. The resulting film was peeled from a glass substrate to prepare a sample having a size of width 2 cm×length 10 cm. Then, the final yellow index (YIf) was determined for the sample using a color meter (Color-Eye 7000A, GRETAGMACBETH), and a change in yellow index (ΔYI) was calculated according to the following Equation (1) to obtain a heat-resistant yellow index, and the results are shown in Table 1 below.
-
Change in Yellow Index (ΔYI)=(Final yellow index (YI f) obtained in Experimental Example 2)−(Yellow index (YI 0) obtained in Experimental Example 1) [Equation 1] -
TABLE 1 Experimental Example Measurement Results of Examples and Comparative Examples Category Yellow index Final yellow index Heat-resistant yellow index (YI0) (YIf) (ΔYI) High temperature curing condition 450° C./ 450° C./ 450° C./ 450° C./ 70 min → 70 min → 70 min → 70 min → 450° C./ 410° C./ 445° C./ 450° C./ 410° C./ 445° C./ 70 min → 60 min → 30 min 70 min → 60 min → 30 min → 450° C./ 410° C./ 445° C./ →445° C./ 410° C./ 445° C./ 445° C./ 70 min 60 min 60 min 30 min 60 min 60 min 30 min Example 1 8.8 9.5 11.3 8.7 0.7 2.5 −0.1 Example 2 12.1 12.0 13.3 15.3 −0.1 1.2 3.2 Example 3 14.1 14.8 16.2 17.6 0.7 2.1 3.5 Comparative 16.8 24.6 39.8 21.3 4.5 7.8 23.0 Example 1 Comparative 15.2 22.5 40.7 21.1 5.9 7.3 25.5 Example 2 Comparative 15.9 23.9 42.5 22.5 6.6 8.0 26.6 Example 3 - As shown in Table 1 above, the polyimide-based resin films of Examples 1 to 3 obtained through a curing process at 450° C. for 70 minutes showed a yellow index (YI0) of 8.8 or more and 14.1 or less. In contrast, the polyimide-based resin films of Comparative Examples 1 to 3 obtained through a curing process at 450° C. for 70 minutes showed a yellow index (YI0) of 15.2 or more and 16.8 or less which is much higher than that of Examples.
- Through this, it was confirmed that the polyimide-based resin films of Examples could have excellent optical properties even during high temperature curing at 400° C. or more.
- In addition, the polyimide-based resin films of Examples 1 to 3 showed a heat resistant yellow index (ΔYI) of −0.1 or more and 3.5 or less, or an absolute value of a change in yellow index (ΔYI) of 0.1 or more and 3.5 or less even when further heat treatment was performed at a high temperature of 400° C. or more.
- On the other hand, when additional heat treatment was performed at a high temperature of 400° C. or more, the polyimide-based resin films of Comparative Examples 1 to 3 showed a heat resistant yellow index (ΔYI) of 4.5 or more and 26.6 or less, or an absolute value of a change in yellow index (ΔYI) of 4.5 or more and 26.6 or less, which was much higher than those of Examples.
- Through this, it was confirmed that the polyimide-based resin films of Examples stably maintained optical properties even during high temperature heat treatment of 400° C. or more.
Claims (18)
Change in Yellow Index (ΔYI)=YI f −YI 0 [Equation 1]
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